Numerically "exact" simulations of entropy production in the fully quantum regime: Boltzmann entropy versus von Neumann entropy

TL;DR

This paper compares Boltzmann and von Neumann entropies in quantum thermodynamics, demonstrating that Boltzmann entropy accurately captures entropy production in strongly coupled quantum systems using numerically exact HEOM simulations.

Contribution

It introduces a scheme using hierarchical equations of motion to evaluate thermodynamic variables and clarifies the proper entropy measure for quantum entropy production.

Findings

Total entropy production is always positive with Boltzmann entropy.

Von Neumann entropy can yield negative entropy production.

Boltzmann entropy is more appropriate for quantum entropy analysis.

Abstract

We present a scheme to evaluate thermodynamic variables for a system coupled to a heat bath under a time-dependent external force using the quasi-static Helmholtz energy from the numerically "exact" hierarchical equations of motion (HEOM). We computed the entropy produced by a spin system strongly coupled to a non-Markovian heat bath for various temperatures. We showed that when changes to the external perturbation occurred sufficiently slowly, the system always reached thermal equilibrium. Thus, we calculated the Boltzmann entropy and the von Neumann entropy for an isothermal process, as well as various thermodynamic variables, such as changes of internal energies, heat, and work, for a system in quasi-static equilibrium based on the HEOM. We found that, although the characteristic features of the system entropies in the Boltzmann and von Neumann cases as a function of the system--bath coupling strength are similar, those for the total entropy production are completely different. The total entropy production in the Boltzmann case is always positive, whereas that in the von Neumann case becomes negative if we chose a thermal equilibrium state of the total system (an unfactorized thermal equilibrium state) as the initial state. This is because the total entropy production in the von Neumann case does not properly take into account the contribution of the entropy from the system--bath interaction. Thus, the Boltzmann entropy must be used to investigate entropy production in the fully quantum regime. Finally, we examined the applicability of the Jarzynski equality.